U.S. patent application number 16/611872 was filed with the patent office on 2021-03-18 for carbazole-based bodipys for organic electroluminescent devices.
The applicant listed for this patent is Merck Patent GmbH. Invention is credited to Tobias GROSSMANN, Dominik JOOSTEN, Jonas KROEBER, Aurelie LUDEMANN, Amir PARHAM.
Application Number | 20210079024 16/611872 |
Document ID | / |
Family ID | 1000005286445 |
Filed Date | 2021-03-18 |
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United States Patent
Application |
20210079024 |
Kind Code |
A1 |
PARHAM; Amir ; et
al. |
March 18, 2021 |
CARBAZOLE-BASED BODIPYS FOR ORGANIC ELECTROLUMINESCENT DEVICES
Abstract
The present invention relates to compounds of the formula (1)
which are suitable for use in electronic devices, in particular
organic electroluminescent devices, and to electronic devices which
comprise these compounds.
Inventors: |
PARHAM; Amir; (Frankfurt am
Main, DE) ; KROEBER; Jonas; (Frankfurt am Main,
DE) ; JOOSTEN; Dominik; (Ober-Ramstadt, DE) ;
LUDEMANN; Aurelie; (Frankfurt am Main, DE) ;
GROSSMANN; Tobias; (Darmstadt, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Merck Patent GmbH |
Darmstadt |
|
DE |
|
|
Family ID: |
1000005286445 |
Appl. No.: |
16/611872 |
Filed: |
May 8, 2018 |
PCT Filed: |
May 8, 2018 |
PCT NO: |
PCT/EP2018/061781 |
371 Date: |
November 8, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/5016 20130101;
H01L 51/5072 20130101; H01L 51/0071 20130101; C07F 5/02 20130101;
H01L 51/5056 20130101; H01L 51/0067 20130101 |
International
Class: |
C07F 5/02 20060101
C07F005/02; H01L 51/00 20060101 H01L051/00; H01L 51/50 20060101
H01L051/50 |
Foreign Application Data
Date |
Code |
Application Number |
May 11, 2017 |
EP |
17170651.8 |
Claims
1. A compound of the formula (1), ##STR00382## where the following
applies to the symbols and indices used: Ar.sup.1 is a heteroaryl
group comprising at least one nitrogen which is represented in
formula (1), having 5 to 30 aromatic ring atoms, which may be
substituted by one or more radicals R.sup.1; Ar.sup.2 stands for an
aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which
may be substituted by one or more radicals R.sup.2; Ar.sup.B is, on
each occurrence, identically or differently, an aromatic or
heteroaromatic ring system having 5 to 60 aromatic ring atoms,
which may be substituted by one or more radicals R.sup.3; X stands,
on each occurrence, identically or differently, for CR.sup.2 or N;
or two adjacent groups X stand for a group of formula (X-1),
##STR00383## where the dashed bonds in formula (X-1) indicate the
bonding of the corresponding adjacent groups X to the structure; V
is on each occurrence, identically or differently, CR.sup.2 or N;
R.sup.1, R.sup.2, R.sup.3 stand on each occurrence, identically or
differently, for H, D, F, Cl, Br, I, CHO, CN, C(.dbd.O)Ar.sup.3,
P(.dbd.O)(Ar.sup.3).sub.2, S(.dbd.O)Ar.sup.3,
S(.dbd.O).sub.2Ar.sup.3, N(Ar.sup.3).sub.2, NO.sub.2,
Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, a
straight-chain alkyl, alkoxy or thioalkyl groups having to 40 C
atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups
having 3 to 40 C atoms, each of which may be substituted by one or
more radicals R.sup.4, where in each case one or more non-adjacent
CH.sub.2 groups may be replaced by R.sup.4C.dbd.CR, C.ident.C,
Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, P(.dbd.O)(R.sup.4), SO, SO.sub.2, O, S or
CONR.sup.4 and where one or more H atoms may be replaced by D, F,
Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring
systems having 5 to 60 aromatic ring atoms, which may in each case
be substituted by one or more radicals R.sup.4, or an aryloxy
groups having 5 to 60 aromatic ring atoms, which may be substituted
by one or more radicals R.sup.4; where two adjacent substituents
R.sup.1, two adjacent substituents R.sup.2 and/or two adjacent
substituents R.sup.3 may form an aliphatic or aromatic ring system
together, which may be substituted by one or more radicals R; and
where one substituent R.sup.1 of the group Ar.sup.1 and one
substituent R.sup.2 of the adjacent 6-membered ring comprising the
groups X may form an aliphatic or aromatic ring system together;
Ar.sup.3 is, on each occurrence, identically or differently, an
aromatic or heteroaromatic ring system having 5 to 60 aromatic ring
atoms, which may in each case also be substituted by one or more
radicals R.sup.4; and R.sup.4 stands on each occurrence,
identically or differently, for H, D, F, Cl, Br, I, CN, a straight
chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms or
branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20
C atoms, where in each case one or more non-adjacent CH.sub.2
groups may be replaced by SO, SO.sub.2, O, S and where one or more
H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or
heteroaromatic ring system having 5 to 24 C atoms.
2. The compound according to claim 1, characterized in that the
group Ar.sup.1 is a heteroaryl group having 5 to 18 aromatic ring
atoms, selected from the groups of formulae (Ar1-1), (Ar1-2) or
(Ar1-3), ##STR00384## where the sign * indicates the position of
the coordination to the Boron and the sign {circumflex over ( )}
indicates the bonds to the adjacent 6-membered ring as depicted in
formula (1); and where Y stands on each occurrence, identically or
differently, for O, S, C(R.sup.1).sub.2 or NR.sup.1; W stands, on
each occurrence, identically or differently, for CR.sup.1 or N; or
two adjacent groups W stand for a group of formula (W-1) or (W-2),
##STR00385## where the dashed bonds in formulae (W-1) and (W-2)
indicate the bonding to the groups of formula (Ar1-1) or (Ar1-2); Z
is on each occurrence, identically or differently, CR.sup.1 or N;
E.sup.1, E.sup.2 are, on each occurrence, identically or
differently, selected from a single bond, B(R.sup.0),
C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C.dbd.O, C.dbd.NR.sup.0,
C.dbd.C(R.sup.0).sub.2, O, S, S.dbd.O, SO.sub.2, N(R.sup.0),
P(R.sup.0) and P(.dbd.O)R.sup.0, where at least one of the groups
E.sup.1 and E.sup.2, present in the same ring, is not a single
bond; R.sup.0 stands on each occurrence, identically or
differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl,
alkoxy or thioalkyl groups having 1 to 40 C atoms or branched or a
cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms,
each of which may be substituted by one or more radicals R.sup.4,
where in each case one or more non-adjacent CH.sub.2 groups may be
replaced by R.sup.4C.dbd.CR, C.dbd.C, Si(R.sup.4).sub.2,
Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, C.dbd., C.dbd.S, C.dbd.Se,
P(.dbd.O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one
or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2,
an aromatic or heteroaromatic ring systems having 5 to 60 aromatic
ring atoms, which may in each case be substituted by one or more
radicals R.sup.4, or an aryloxy groups having 5 to 60 aromatic ring
atoms, which may be substituted by one or more radicals R.sup.4,
where two adjacent substituents R.sup.0 may form an aliphatic or
aromatic ring system together, which may be substituted by one or
more radicals R.sup.4; and R.sup.1 has the same meaning as in claim
1.
3. The compound according to claim 2, characterized in that the
compound is selected from the compounds of formulae (2) to (5) as
listed below: ##STR00386## where the symbols Ar.sup.2 stands for an
aryl or heteroaryl group having 5 to 30 aromatic ring atoms which
may be substituted by one or more radicals R.sup.2; Ar.sup.B is, on
each occurrence, identically or differently, an aromatic or
heteroaromatic ring system having 5 to 60 aromatic ring atoms which
may be substituted by one or more radicals R.sup.3; X stands, on
each occurrence, identically or differently for CR.sup.2 or N; or
two adjacent groups X stand for a group of formula (X-1),
##STR00387## where the dashed bonds in formula (X-1) indicate the
bonding of the corresponding adjacent groups X to the structure;
and the symbols W and Y have the same meaning as in claim 2; and
where E stands for --B(R.sup.0)--, --C(R.sup.0).sub.2--,
--Si(R.sup.0).sub.2--, --C(.dbd.O)--, --C(.dbd.NR.sup.0)--,
--C(R.sup.0).dbd.C(R.sup.0)--, --C(.dbd.C(R.sup.0).sub.2)--, --O--,
--S--, --S(.dbd.O)--, --SO.sub.2--, --N(R.sup.0)--, --P(R.sup.0)--
or --P((.dbd.O)R.sup.0)--, where R.sup.0 has the same meaning as in
claim 2.
4. The compound according to claim 1, characterized in that the
compound is selected from the compounds of formulae (1-1) to (3-9)
as listed below, ##STR00388## ##STR00389## ##STR00390##
##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395##
##STR00396## ##STR00397## where the symbols X and Ar.sup.B have the
same meaning as in claim 1, Y stands on each occurrence,
identically or differently, for O, S, C(R.sup.1).sub.2 or NR.sup.1;
W stands, on each occurrence, identically or differently, for
CR.sup.1 or N; or two adjacent groups W stand for a group of
formula (W-1) or (W-2 ##STR00398## where the dashed bonds in
formulae (W-1) and (W-2) indicate the bonding to the groups of
formula (Ar-1) or (Ar1-2); Z is on each occurrence, identically or
differently, CR.sup.1 or N; E.sup.1, E.sup.2 are, on each
occurrence, identically or differently, selected from a single
bond, B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C.dbd.O,
C.dbd.NR.sup.0, C.dbd.C(R.sup.0).sub.2, O, S, S.dbd.O, SO.sub.2,
N(R.sup.0), P(R.sup.0) and P(.dbd.O)R.sup.0, where at least one of
the groups E.sup.1 and E.sup.2, present in the same ring, is not a
single bond; R.sup.0 stands on each occurrence, identically or
differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl,
alkoxy or thioalkyl groups having 1 to 40 C atoms or branched or a
cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms,
each of which may be substituted by one or more radicals R.sup.4,
where in each case one or more non-adjacent CH.sub.2 groups may be
replaced by R.sup.4C.dbd.CR.sup.4, C.ident.C, Si(R.sup.4).sub.2,
Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
P(.dbd.O)(R.sup.4), SO, SO.sub.2, O, S or CONR.sup.4 and where one
or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2,
an aromatic or heteroaromatic ring systems having 5 to 60 aromatic
ring atoms which may in each case be substituted by one or more
radicals R.sup.4, or an aryloxy groups having 5 to 60 aromatic ring
atoms, which may be substituted by one or more radicals R.sup.4,
where two adjacent substituents R.sup.0 may form an aliphatic or
aromatic ring system together, which may be substituted by one or
more radicals R.sup.4; and the symbol E stands for --B(R.sup.0)--,
--C(R.sup.0).sub.2--, --Si(R.sup.0).sub.2--, --C(.dbd.O)--,
--C(.dbd.NR.sup.0)--, --C(R.sup.0).dbd.C(R.sup.0)--,
--C(.dbd.C(R.sup.0).sub.2)--, --O--, --S--, --S(.dbd.O)--,
--SO.sub.2--, --N(R.sup.0)--, --P(R.sup.0)-- and
--P((.dbd.O)R.sup.0)--.
5. The compound according to claim 4, characterized in that there
are maximum two X groups per 6-membered ring, which stand for N,
there are maximum two W groups per 6-membered ring, which stand for
N, there are maximum two V groups per 6-membered ring, which stand
for N and there are maximum two Z groups per 6-membered ring, which
stand for N.
6. The compound according to claim 1, characterized in that the
compound is selected from the compounds of formulae (1-1a) to
(3-9a), ##STR00399## ##STR00400## ##STR00401## ##STR00402##
##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407##
##STR00408## ##STR00409## ##STR00410## where the symbols R.sup.1,
R.sup.2 and Ar.sup.B have the same meaning as given in claim 1, Y
stands on each occurrence, identically or differently, for O, S,
C(R.sup.1).sub.2 or NR.sup.1; E stands for --B(R.sup.0)--,
--C(R.sup.0).sub.2--, --Si(R.sup.0).sub.2--, --C(.dbd.O)--,
--C(.dbd.NR.sup.0)--, --C(R.sup.0).dbd.C(R.sup.0)--,
--C(.dbd.C(R.sup.0).sub.2)--, --O--, --S--, --S(.dbd.O)--,
--SO.sub.2--, --N(R.sup.0)--, --P(R.sup.0)-- and
--P((.dbd.O)R.sup.0)-- and R.sup.0 stands on each occurrence,
identically or differently, for H, D, F, Cl, Br, I, CN, a
straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C
atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups
having 3 to 40 C atoms, each of which may be substituted by one or
more radicals R.sup.4, where in each case one or more non-adjacent
CH.sub.2 groups may be replaced by R.sup.4C.dbd.CR.sup.4,
C.ident.C, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, P(.dbd.O)(R.sup.4), SO, SO.sub.2, O, S
or CONR.sup.4 and where one or more H atoms may be replaced by D,
F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring
systems having 5 to 60 aromatic ring atoms, which may in each case
be substituted by one or more radicals R.sup.4, or an aryloxy
groups having 5 to 60 aromatic ring atoms, which may be substituted
by one or more radicals R.sup.4, where two adjacent substituents
R.sup.0 may form an aliphatic or aromatic ring system together,
which may be substituted by one or more radicals R.sup.4.
7. The compound according to claim 1, characterized in that the
group Ar.sup.B is selected from aromatic or heteroaromatic ring
systems having 5 to 18 C atoms, each of which may be substituted by
one or more radicals R.sup.3.
8. The compound according to claim 1, characterized in that the
compound comprises at least one group R.sup.1 or R.sup.2 selected
from aromatic or heteroaromatic ring systems having 5 to 60
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.4.
9. The compound according to claim 1, characterized in that the
compound comprises at least one group R.sup.1 or R.sup.2 selected
from the groups of formula (R-1) to (R-15), ##STR00411##
##STR00412## ##STR00413## where the dashed bond indicates the
bonding to the structure of formula (1) and the symbol V has the
same meaning as in claim 1, with the proviso that V is a C atom
when the dashed bond is bonded to V, and where: R.sup.N, R.sup.C
are on each occurrence, identically or differently, H, D, F, Cl,
Br, I, CHO, N(Ar.sup.3).sub.2, C(.dbd.O)Ar.sup.3,
(P(.dbd.O)(Ar.sup.3).sub.2, S(.dbd.O)Ar.sup.3, S(O).sub.2Ar.sup.3,
(R)C.dbd.C(R)Ar.sup.3, CN, NO.sub.2, Si(R.sup.4).sub.3,
B(OR.sup.4).sub.2, B(R.sup.4).sub.2, B(N(R.sup.4).sub.2).sub.2,
OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkoxy
group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl
group having 2 to 40 C atoms or a branched or cyclic alkyl,
alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C
atoms, each of which may be substituted by one or more radicals
R.sup.4, where one or more, preferably non-adjacent CH.sub.2 groups
may be replaced by (R.sup.4)C.dbd.C(R.sup.4), C.ident.C,
Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, (Sn(R.sup.4).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, P(.dbd.O)(R.sup.4), SO, SO.sub.2, N(R.sup.4), O,
S or a CON(R.sup.4) and where one or more H atoms may be replaced
by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or
heteroaromatic ring system having 5 to 60 aromatic ring atoms,
which may in each case be substituted by one or more radicals
R.sup.4, or an aryloxy or heteroaryloxy group having 5 to 60
aromatic ring atoms, which may be substituted by one or more
radicals R.sup.4, where optionally two adjacent substituents
R.sup.C can form a mono- or polycyclic, aliphatic, aromatic or
heteroaromatic ring system with one another; where Ar.sup.3 and
R.sup.4 have the same definitions as in claim 1; and T stands, on
each occurrence, identically or differently, for CR.sup.4 or N,
with the proviso that T is a C atom when the dashed bond is bonded
to T; or two adjacent groups T stand fora group of formula (T-1) or
(T-2), ##STR00414## where the dashed bonds in formulae (T-1) and
(T-2) indicate the bonding to the groups of formulae (R-1) to
(R-5); G is on each occurrence, identically or differently,
CR.sup.4 or N; where R.sup.4 has the same meaning as in claim 1; L
is an aromatic or heteroaromatic ring system having 5 to 30
aromatic ring atoms, which may be substituted by one or more
radicals R.sup.4; and n is 0 or 1.
10. A formulation comprising at least one compound according to
claim 1 and at least one solvent.
11. A process for the preparation of the compound of formula (1)
according to claim 1, characterized in that it comprises the
following steps: a) A heteroaromatic group Ar.sup.1 comprising at
least one nitrogen is bonded to a heterocycle comprising a pyrrole
moiety via a C--C coupling in order to obtain a compound of formula
Int: ##STR00415## b) The compound of formula Int reacts with a
triarylborane B(Ar.sup.B).sub.3 so that a compound of formula (1)
is obtained: ##STR00416## where the symbols Ar.sup.1, Ar.sup.2,
Ar.sup.B and X have the same meaning as in claim 1.
12. An electronic device comprising at least one compound according
to claim 1.
13. The electronic device according to claim 12, characterized in
that it is selected from the group consisting of organic
electroluminescent devices, organic integrated circuits, organic
field-effect transistors, organic thin-film transistors, organic
light-emitting transistors, organic solar cells, dye-sensitised
organic solar cells, organic optical detectors, organic
photoreceptors, organic field-quench devices, light-emitting
electrochemical cells, organic laser diodes and organic plasmon
emitting devices.
14. An electronic device which is an organic electroluminescent
device, characterised in that the compound according to claim 1 is
employed as a matrix material for emitters, a
hole-transport-material or an electron-transport material.
15. An electronic device characterized in that the device is
organic electroluminescent devices comprising a cathode, an anode
and at least one emitting layer arranged between the anode and the
cathode, wherein the at least one emitting layer comprises at least
one phosphorescent material as an emitter and at least one compound
according to claim 1 as a matrix material.
16. The electronic device according to claim 15, characterized in
that the phosphorescent material has an emission wavelength
comprised between 550 nm to 680 nm.
Description
[0001] The present invention relates to a compound of the formula
(1), to the use of the compound in an electronic device, and to an
electronic device comprising a compound of the formula (1). The
present invention furthermore relates to a process for the
preparation of a compound of the formula (1) and to a formulation
comprising one or more compounds of the formula (1).
[0002] The structure of organic electroluminescent devices (OLEDs)
in which organic semiconductors are employed as functional
materials is described, for example, in U.S. Pat. No. 4,539,507.
The emitting materials employed here are very often organometallic
complexes which exhibit phosphorescence. For quantum-mechanical
reasons, an up to four-fold increase in efficiency is possible
using phosphorescent instead of fluorescent emitters. In general,
however, there is still a need for improvement in the case of
OLEDs, in particular also in the case of OLEDs which exhibit
triplet emission (phosphorescence), for example with respect to
efficiency, operating voltage and lifetime.
[0003] The properties of phosphorescent OLEDs are not only
determined by the triplet emitters employed but also by the other
materials used together with triplet emitters in OLEDs, such as
matrix materials, also called host materials. Improvements in these
materials and their charge-transport properties can thus also
result in significant improvements in the OLED properties.
[0004] Thus, the choice of the matrix material in an emission layer
comprising a phosphorescent emitter has a great influence on OLEDs
properties, especially in terms of efficiency. The matrix material
limits the quenching of excited states of emitter molecules by
energy transfer.
[0005] The object of the present invention is the provision of
compounds, which are suitable for use in an OLED, in particular as
matrix material for phosphorescent emitters. A further object of
the present invention is to provide further organic semiconductors
for organic electroluminescent devices to provide the person
skilled in the art with a greater possible choice of materials for
the production of OLEDs.
[0006] Organoboron complexes are known from the prior art for their
optical properties (for example in Mes-Montoya et al., J. Org.
Chem. 2016, 81, 3296-3302 and in Liu et al., Adv. Funct. Mater.
2005, 15, No. 1, January, 143-154).
[0007] Surprisingly, it has been found that certain organoboron
complexes described in greater detail below are highly suitable for
use in OLEDs, in particular as matrix material for phosphorescent
emitters. When employed as matrix materials, these compounds lead
to OLEDs exhibiting very good properties in terms of lifetime
and/or efficiency and/or electroluminescent emission. In addition,
these compounds have a high glass transition temperature and a good
thermal stability, which is an important property for OLED
materials, especially when the materials are vapor-deposited via a
vacuum process.
[0008] The present invention therefore relates to these compounds
and to electronic devices, in particular organic electroluminescent
devices, which comprise compounds of this type.
[0009] The present invention relates to a compound of the formula
(1):
##STR00001##
where the following applies to the symbols and indices used:
Ar.sup.1 is a heteroaryl group comprising at least one nitrogen
which is represented in formula (1), having 5 to 30 aromatic ring
atoms, which may be substituted by one or more radicals R.sup.1;
Ar.sup.2 stands for an aryl or heteroaryl group having 5 to 30
aromatic ring atoms, which may be substituted by one or more
radicals R.sup.2; Ar.sup.B is, on each occurrence, identically or
differently, an aromatic or heteroaromatic ring system having 5 to
60 aromatic ring atoms, which may be substituted by one or more
radicals R.sup.3; X stands, on each occurrence, identically or
differently, for CR.sup.2 or N; or two adjacent groups X stand for
a group of formula (X-1),
##STR00002##
where the dashed bonds in formula (X-1) indicate the bonding of the
corresponding adjacent groups X to the structure of formula (1); V
is on each occurrence, identically or differently, CR.sup.2 or N;
R.sup.1, R.sup.2, R.sup.3 stand on each occurrence, identically or
differently, for H, D, F, C, Br, I, CHO, CN, C(.dbd.O)Ar.sup.3,
P(.dbd.O)(Ar.sup.3).sub.2, S(.dbd.O)Ar.sup.3,
S(.dbd.O).sub.2Ar.sup.3, N(Ar.sup.3).sub.2, NO.sub.2,
Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, a
straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C
atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups
having 3 to 40 C atoms, each of which may be substituted by one or
more radicals R.sup.4, where in each case one or more non-adjacent
CH.sub.2 groups may be replaced by R.sup.4C.dbd.CR.sup.4,
C.ident.C, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, P(.dbd.O)(R.sup.4), SO, SO.sub.2, O, S
or CONR.sup.4 and where one or more H atoms may be replaced by D,
F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring
systems having 5 to 60 aromatic ring atoms, which may in each case
be substituted by one or more radicals R.sup.4, or an aryloxy
groups having 5 to 60 aromatic ring atoms, which may be substituted
by one or more radicals R.sup.4; where two adjacent substituents
R.sup.1, two adjacent substituents R.sup.2 and/or two adjacent
substituents R.sup.3 may form an aliphatic or aromatic ring system
together, which may be substituted by one or more radicals R.sup.4;
and where one substituent R.sup.1 of the group Ar.sup.1 and one
substituent R.sup.2 of the adjacent 6-membered ring comprising the
groups X may form an aliphatic or aromatic ring system together;
Ar.sup.3 is, on each occurrence, identically or differently, an
aromatic or heteroaromatic ring system having 5 to 60 aromatic ring
atoms, which may in each case also be substituted by one or more
radicals R.sup.4; R.sup.4 stands on each occurrence, identically or
differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl,
alkoxy or thioalkyl groups having 1 to 20 C atoms or branched or
cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms,
where in each case one or more non-adjacent CH.sub.2 groups may be
replaced by SO, SO.sub.2, O, S and where one or more H atoms may be
replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic
ring system having 5 to 24 C atoms.
[0010] Adjacent substituents in the sense of the present invention
are substituents which are bonded to carbon atoms which are linked
directly to one another or which are bonded to the same carbon
atom.
[0011] Furthermore, the following definitions of chemical groups
apply for the purposes of the present application:
[0012] An aryl group in the sense of this invention contains 6 to
60 aromatic ring atoms; a heteroaryl group in the sense of this
invention contains 5 to 60 aromatic ring atoms, at least one of
which is a heteroatom. The hetero atoms are preferably selected
from N, O and S. This represents the basic definition. If other
preferences are indicated in the description of the present
invention, for example with respect to the number of aromatic ring
atoms or the heteroatoms present, these apply.
[0013] An aryl group or heteroaryl group here is taken to mean
either a simple aromatic ring, i.e. benzene, or a simple
heteroaromatic ring, for example pyridine, pyrimidine or thiophene,
or a condensed (annellated) aromatic or heteroaromatic polycycle,
for example naphthalene, phenanthrene, quinoline or carbazole. A
condensed (annellated) aromatic or heteroaromatic polycycle in the
sense of the present application consists of two or more simple
aromatic or heteroaromatic rings condensed with one another.
[0014] An aryl or heteroaryl group, which may in each case be
substituted by the above-mentioned radicals and which may be linked
to the aromatic or heteroaromatic ring system via any desired
positions, is taken to mean, in particular, groups derived from
benzene, naphthalene, anthracene, phenanthrene, pyrene,
dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene,
benzophenanthrene, tetracene, pentacene, benzopyrene, furan,
benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene,
isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole,
carbazole, pyridine, quinoline, isoquinoline, acridine,
phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,
benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole,
indazole, imidazole, benzimidazole, naphthimidazole,
phenanthrimidazole, pyridimidazole, pyrazinimidazole,
quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole,
anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,
1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,
pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine,
naphthyridine, azacarbazole, benzocarboline, phenanthroline,
1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,
1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,
1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,
1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,
tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,
purine, pteridine, indolizine and benzothiadiazole.
[0015] An aryloxy group in accordance with the definition of the
present invention is taken to mean an aryl group, as defined above,
which is bonded via an oxygen atom. An analogous definition applies
to heteroaryloxy groups.
[0016] An aromatic ring system in the sense of this invention
contains 6 to 60 C atoms in the ring system. A heteroaromatic ring
system in the sense of this invention contains 5 to 60 aromatic
ring atoms, at least one of which is a heteroatom. The heteroatoms
are preferably selected from N, O and/or S. An aromatic or
heteroaromatic ring system in the sense of this invention is
intended to be taken to mean a system which does not necessarily
contain only aryl or heteroaryl groups, but instead in which, in
addition, a plurality of aryl or heteroaryl groups may be connected
by a non-aromatic unit (preferably less than 10% of the atoms other
than H), such as, for example, an sp.sup.3-hybridised C, Si, N or O
atom, an sp.sup.2-hybridised C or N atom or an sp-hybridised C
atom. Thus, for example, systems such as 9,9'-spirobifluorene,
9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc.,
are also intended to be taken to be aromatic ring systems in the
sense of this invention, as are systems in which two or more aryl
groups are connected, for example, by a linear or cyclic alkyl,
alkenyl or alkynyl group or by a silyl group. Furthermore, systems
in which two or more aryl or heteroaryl groups are linked to one
another via single bonds are also taken to be aromatic or
heteroaromatic ring systems in the sense of this invention, such
as, for example, systems such as biphenyl, terphenyl or
diphenyltriazine.
[0017] An aromatic or heteroaromatic ring system having 5-60
aromatic ring atoms, which may in each case also be substituted by
radicals as defined above and which may be linked to the aromatic
or heteroaromatic group via any desired positions, is taken to
mean, in particular, groups derived from benzene, naphthalene,
anthracene, benzanthracene, phenanthrene, benzophenanthrene,
pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene,
benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene,
quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene,
dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene,
truxene, isotruxene, spirotruxene, spiroisotruxene, furan,
benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene,
isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole,
carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline,
isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline,
benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine,
phenoxazine, pyrazole, indazole, imidazole, benzimidazole,
naphthimidazole, phenanthrimidazole, pyridimidazole,
pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,
naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,
1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine,
benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline,
1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene,
1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,
4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,
phenothiazine, fluorubin, naphthyridine, azacarbazole,
benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole,
benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,
1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,
1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole,
1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole,
1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine,
pteridine, indolizine and benzothiadiazole, or combinations of
these groups.
[0018] For the purposes of the present invention, a straight-chain
alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl
group having 3 to 40 C atoms or an alkenyl or alkynyl group having
2 to 40 C atoms, in which, in addition, individual H atoms or
CH.sub.2 groups may be substituted by the groups mentioned above
under the definition of the radicals, is preferably taken to mean
the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl,
neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl,
n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl,
pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,
pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,
cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl,
pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1
to 40 C atoms is preferably taken to mean methoxy,
trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,
s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,
cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,
cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy,
2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio,
i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,
n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio,
n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio,
2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio,
2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio,
pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio,
heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio,
ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio,
heptynylthio or octynylthio.
[0019] The formulation that two radicals may form a ring with one
another is, for the purposes of the present application, intended
to be taken to mean, inter alia, that the two radicals are linked
to one another by a chemical bond. This is illustrated by the
following schemes:
##STR00003##
[0020] Furthermore, the above-mentioned formulation is also
intended to be taken to mean that, in the case where one of the two
radicals represents hydrogen, the second radical is bonded at the
position to which the hydrogen atom was bonded, with formation of a
ring. This is illustrated by the following scheme:
##STR00004##
[0021] In accordance with the invention, one substituent R.sup.1 of
the group Ar.sup.1 and one substituent R.sup.2 of the adjacent
6-membered ring comprising the groups X as depicted in formula (1)
may form an aliphatic or aromatic ring system together. The
following formula (1-E) is an example of the case, where one
substituent R.sup.1 and one substituent R.sup.2 form an aliphatic
ring system with one another, corresponding to a divalent bridge E
as follows:
##STR00005##
where E is a divalent bridge and E stands for --B(R.sup.0)--,
--C(R.sup.0).sub.2--, --Si(R.sup.0).sub.2--, --C(.dbd.O)--,
--C(.dbd.NR.sup.0)--, --C(R.sup.0).dbd.C(R.sup.0)--,
--C(.dbd.C(R.sup.0).sub.2)--, --O--, --S--, --S(.dbd.O)--,
--SO.sub.2--, --N(R.sup.0)--, --P(R.sup.0)-- and
--P((.dbd.O)R.sup.0)--; and R.sup.0 stands on each occurrence,
identically or differently, for H, D, F, Cl, Br, I, CN, a
straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C
atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups
having 3 to 40 C atoms, each of which may be substituted by one or
more radicals R.sup.4, where in each case one or more non-adjacent
CH.sub.2 groups may be replaced by R.sup.4C.dbd.CR.sup.4,
C.ident.C, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, P(.dbd.O)(R.sup.4), SO, SO.sub.2, O, S
or CONR.sup.4 and where one or more H atoms may be replaced by D,
F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring
systems having 5 to 60 aromatic ring atoms, which may in each case
be substituted by one or more radicals R.sup.4, or an aryloxy
groups having 5 to 60 aromatic ring atoms, which may be substituted
by one or more radicals R.sup.4, where two adjacent substituents
R.sup.0 may form an aliphatic or aromatic ring system together,
which may be substituted by one or more radicals R.sup.4.
[0022] Preferably, E stands for --C(R.sup.0).sub.2--,
--C(R.sup.0).dbd.C(R.sup.0)--, --O--, --S-- or --N(R.sup.0)--. Very
preferably, E stands for --C(R.sup.0).sub.2--, or
--N(R.sup.0)--.
[0023] Preferably, R.sup.0 stands on each occurrence, identically
or differently, for H, D, F, a straight-chain alkyl group having 1
to 10 C atoms or branched or a cyclic alkyl group having 3 to 10 C
atoms, each of which may be substituted by one or more radicals
R.sup.4, where one or more H atoms may be replaced by D or F, an
aromatic or heteroaromatic ring systems having 5 to 18 aromatic
ring atoms, which may in each case be substituted by one or more
radicals R.sup.4, where two adjacent substituents R.sup.0 may form
an aliphatic or aromatic ring system together, which may be
substituted by one or more radicals R.sup.4.
[0024] In accordance with a preferred embodiment of the invention,
the group Ar.sup.1 is a heteroaryl group having 5 to 18 aromatic
ring atoms, selected from the groups of formulae (Ar1-1), (Ar1-2)
or (Ar1-3),
##STR00006##
where the sign * indicates the position of the coordination to the
Boron and the sign {circumflex over ( )} indicates the bonds to the
adjacent 6-membered ring as depicted in formula (1); and where
[0025] Y stands on each occurrence, identically or differently, for
O, S, C(R.sup.1).sub.2 or NR.sup.1; [0026] W stands, on each
occurrence, identically or differently, for CR.sup.1 or N; or two
adjacent groups W stand for a group of formula (W-1) or (W-2),
[0026] ##STR00007## [0027] where the dashed bonds in formulae (W-1)
and (W-2) indicate the bonding to the groups of formula (Ar1-1) or
(Ar1-2); [0028] Z is on each occurrence, identically or
differently, CR.sup.1 or N; [0029] E.sup.1, E.sup.2 are, on each
occurrence, identically or differently, selected from a single
bond, B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C.dbd.O,
C.dbd.NR.sup.0, C.dbd.C(R.sup.0).sub.2, O, S, S.dbd.O, SO.sub.2,
N(R.sup.0), P(R.sup.0) and P(.dbd.O)R.sup.0, where at least one of
the groups E.sup.1 and E.sup.2, present in the same ring, is not a
single bond; and [0030] R.sup.1 and R.sup.0 have the same meaning
as above.
[0031] Preferably, E.sup.1, E.sup.2 are, on each occurrence,
identically or differently, selected from a single bond,
C(R.sup.0).sub.2, C.dbd.O, O, S, S.dbd.O, SO.sub.2 and N(R.sup.0),
where at least one of the groups E.sup.1 and E.sup.2, present in
the same ring, is not a single bond. Very preferably, one of the
groups E.sup.1 and E.sup.2 is a single bond and the other group is
C(R.sup.0).sub.2, C.dbd.O, O, S, S.dbd.O, SO.sub.2 or N(R.sup.0).
Particularly preferably, one of the groups E.sup.1 and E.sup.2 is a
single bond and the other one is C(R.sup.0).sub.2, O, S, or
N(R.sup.0).
[0032] In accordance with a preferred embodiment, the compound of
formula (1) is selected from the compounds of formulae (2) to (5)
as listed below:
##STR00008##
where the symbols E, Ar.sup.2, Ar.sup.B, X, W and Y have the same
meaning as above.
[0033] In accordance with a preferred embodiment, the compound of
formula (1) is selected from the compounds of formulae (1-1) to
(3-9) as listed below,
##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013##
##STR00014## ##STR00015## ##STR00016## ##STR00017##
where the symbols Ar.sup.B, E, W, Y and X have the same meaning as
above.
[0034] Preferably, there are maximum two groups X per 6-membered
ring, which stand for N, there are maximum two groups W per
6-membered ring, which stand for N, there are maximum two groups V
per 6-membered ring, which stand for N and there are maximum two
groups Z per 6-membered ring, which stand for N.
[0035] In accordance with a preferred embodiment, the compounds of
formula (1) and (1-1) to (3-9) are selected from the compounds of
formulae (1-1a) to (3-9a),
##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027##
where the symbols R.sup.1, R.sup.2, Ar.sup.B, E, E.sup.1, E.sup.2
and Y have the same meaning as above.
[0036] In accordance with a preferred embodiment, the group
Ar.sup.B is, on each occurrence, identically or differently, an
aromatic or heteroaromatic ring system having 5 to 30 aromatic ring
atoms, more preferably 5 to 18 aromatic ring atoms, which may be
substituted by one or more radicals R.sup.3. It is very preferably
that Ar.sup.B is, on each occurrence, identically or differently,
an aromatic ring system having 6 to 18 aromatic ring atoms, more
preferably 6 to 12 aromatic ring atoms, which may be substituted by
one or more radicals R.sup.3. Examples of very suitable groups for
Ar.sup.B are phenyl, biphenyl and naphthyl groups, which may be
substituted by one or more radicals R.sup.3.
[0037] Preferably, R.sup.1, R.sup.2 stand on each occurrence,
identically or differently, for H, D, F, CN, N(Ar.sup.3).sub.2, a
straight-chain alkyl group having 1 to 20 C atoms or branched or a
cyclic alkyl group having 3 to 20 C atoms, each of which may be
substituted by one or more radicals R.sup.4, where in each case one
or more non-adjacent CH.sub.2 groups may be replaced by
R.sup.4C.dbd.CR.sup.4, C.dbd.O, O or S and where one or more H
atoms may be replaced by D or F, an aromatic or heteroaromatic ring
systems having 5 to 40 aromatic ring atoms, preferably 5 to 25
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.4; where two adjacent substituents R.sup.1
and/or two adjacent substituents R.sup.2 may form an aliphatic or
aromatic ring system together, which may be substituted by one or
more radicals R.sup.4.
[0038] Preferably, R.sup.3 stands on each occurrence, identically
or differently, for H, D, F, CN, N(Ar.sup.3).sub.2, a
straight-chain alkyl group having 1 to 20 C atoms or branched or a
cyclic alkyl group having 3 to 20 C atoms, each of which may be
substituted by one or more radicals R.sup.4, where in each case one
or more non-adjacent CH.sub.2 groups may be replaced by
R.sup.4C.dbd.CR.sup.4, C.dbd.O, O or S and where one or more H
atoms may be replaced by D or F, an aromatic or heteroaromatic ring
systems having 5 to 40 aromatic ring atoms, preferably 5 to 25
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.4; where two adjacent substituents R.sup.3
may form an aliphatic or aromatic ring system together, which may
be substituted by one or more radicals R.sup.4. Very preferably,
R.sup.3 stands on each occurrence, identically or differently, for
H, D, F, a straight-chain alkyl group having 1 to 10 C atoms or
branched or a cyclic alkyl group having 3 to 10 C atoms, each of
which may be substituted by one or more radicals R.sup.4, where one
or more H atoms may be replaced by D or F, an aromatic or
heteroaromatic ring systems having 5 to 40 aromatic ring atoms,
preferably 5 to 25 aromatic ring atoms, very preferably 5 to 18
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.4.
[0039] In accordance with a preferred embodiment, the compounds of
formulae (1), (1-1) to (3-9) and (1-1a) to (3-9a) comprise at least
one group R.sup.1 or R.sup.2 selected from aromatic or
heteroaromatic ring systems having 5 to 60 aromatic ring atoms,
preferably 5 to 40 aromatic rings atoms, more preferably 5 to 25
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.4.
[0040] More preferably, the compounds of formulae (1), (1-1) to
(3-9), (1-1a) to (3-9a) comprise at least one group R.sup.1 or
R.sup.2 selected from the groups of formulae (R-1) to (R-15),
##STR00028## ##STR00029## ##STR00030##
where: the dashed bond indicates the bonding to the structure of
formulae (1), (1-1) to (3-9) or (1-1a) to (3-9a) and the symbol V
has the same meaning as above, with the proviso that V is a C atom
when the dashed bond is bonded to V, and where: R.sup.N, R.sup.C
are on each occurrence, identically or differently, H, D, F, Cl,
Br, I, CHO, N(Ar.sup.3).sub.2, C(.dbd.O)Ar.sup.3,
P(.dbd.O)(Ar.sup.3).sub.2, S(.dbd.O)Ar.sup.3,
S(.dbd.O).sub.2Ar.sup.3, (R.sup.4)C.dbd.C(R.sup.4)Ar.sup.3, CN,
NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, B(R.sup.4).sub.2,
B(N(R.sup.4).sub.2).sub.2, OSO.sub.2R.sup.4, a straight-chain
alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a
straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a
branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy
group having 3 to 40 C atoms, each of which may be substituted by
one or more radicals R.sup.4, where one or more, preferably
non-adjacent CH.sub.2 groups may be replaced by
(R.sup.4)C.dbd.C(R.sup.4), C.ident.C, Si(R.sup.4).sub.2,
Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
P(.dbd.O)(R.sup.4), SO, SO.sub.2, N(R.sup.4), 0, S or CON(R.sup.4)
and where one or more H atoms may be replaced by D, F, Cl, Br, I,
CN or NO.sub.2, or an aromatic or heteroaromatic ring system having
5 to 60 aromatic ring atoms, which may in each case be substituted
by one or more radicals R.sup.4, or an aryloxy or heteroaryloxy
group having 5 to 60 aromatic ring atoms, which may be substituted
by one or more radicals R.sup.4, where optionally two adjacent
substituents R.sup.C can form a mono- or polycyclic, aliphatic,
aromatic or heteroaromatic ring system with one another; where
Ar.sup.3 and R.sup.4 have the same definitions as above; and T
stands, on each occurrence, identically or differently, for
CR.sup.4 or N, with the proviso that T is a C atom when the dashed
bond is bonded to T; or two adjacent groups T stand for a group of
formula (T-1) or (T-2),
##STR00031##
where the dashed bonds in formulae (T-1) and (T-2) indicate the
bonding to the groups of formulae (R-1) to (R-5); G is on each
occurrence, identically or differently, CR.sup.4 or N; where
R.sup.4 has the same meaning as above; L is an aromatic or
heteroaromatic ring system having 5 to 30 aromatic ring atoms,
which may be substituted by one or more radicals R.sup.4; n is 0 or
1, preferably 0. L is preferably an aromatic or heteroaromatic ring
system having 5 to 18 aromatic atoms, which may be substituted by
one or more radicals R.sup.4. L is very preferably an aromatic ring
system having 6 to 12 aromatic atoms, which may be substituted by
one or more radicals R.sup.4. L is particularly preferably a phenyl
group, which may be substituted by one or more radicals
R.sup.4.
[0041] Examples of suitable groups R.sup.1 or R.sup.2 of formulae
(R-1) to (R-15) are groups of formulae (R-16) to (R-129),
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051##
##STR00052## ##STR00053##
where the dashed bond indicates the bonding to the group of
formulae (1), (1-1) to (3-9) or (1-1a) to (3-9a); E, R.sup.N and
R.sup.C have the same meaning as above; and the groups of formulae
(R-16) to (R-129) are optionally substituted by one or more
radicals R.sup.4 at any free positions.
[0042] Among formulae (R-1) to (R-15), formulae (R-1), (R-2),
(R-4), (R-5) and (R-8) to (R-12) are preferred.
[0043] Among formulae (R-16) to (R-129), formulae (R-16), (R-19),
(R-22) to (R-33), (R-42), (R-44), (R-55), (R-56), (R-68), (R-71),
(R-72), (R-76) to (R-78), (R-93), (R-94), (R-96), (R-101) to
(R-108), (R-120), (R-123), (R-125), (R-126), (R-128) and (R-129)
are preferred.
[0044] The group R.sup.C according to the present invention is
preferably selected on each occurrence, identically or differently,
from the group consisting of H, D, F, CN, Si(R.sup.4).sub.3, a
straight-chain alkyl group having 1 to 10 C atoms or a branched or
cyclic alkyl group having 3 to 10 C atoms, each of which may be
substituted by one or more radicals R.sup.4, an aromatic or
heteroaromatic group having 5 to 25 aromatic ring atoms, each of
which may be substituted by one or more radicals R.sup.4, where two
adjacent substituents R.sup.C may optionally form a mono- or
polycyclic, aliphatic ring system or aromatic ring system, each of
which may be substituted by one or more radicals R.sup.4. More
preferably, R.sup.C is selected on each occurrence, identically or
differently, from the group consisting of H, a straight-chain alkyl
group having 1 to 5 C atoms or a branched or cyclic alkyl group
having 3 to 5 C atoms, each of which may be substituted by one or
more radicals R.sup.4, an aryl or heteroaryl group having 5 to 18
aromatic ring atoms, each of which may be substituted by one or
more radicals R.sup.4.
[0045] The group R.sup.N according to the invention is preferably
selected on each occurrence, identically or differently, from the
group consisting of a straight-chain alkyl group having 1 to 10 C
atoms or a branched or cyclic alkyl group having 3 to 10 C atoms,
each of which may be substituted by one or more radicals R.sup.4,
an aromatic or heteroaromatic ring system having 5 to 25 aromatic
ring atoms, each of which may be substituted by one or more
radicals R.sup.4. More preferably, R.sup.N is an aromatic or
heteroaromatic ring system having 5 to 25 aromatic ring atoms,
preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13
aromatic ring atoms. The group R.sup.N is particularly preferably
selected from the group consisting of phenyl, biphenyl, terphenyl,
pyridine, quinoline, isoquinoline, pyridazine, benzopyridazine,
pyrimidine, benzopyrimidine, benzimidazole, quinoxaline, pyrazine,
1,3,5-triazine, 1,2,4-triazine or 1,2,3-triazine, each of which may
be substituted by one or more radicals R.sup.4.
[0046] Examples of suitable compounds according to the invention
are the structures shown in the table below:
TABLE-US-00001 ##STR00054## ##STR00055## ##STR00056## ##STR00057##
##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062##
##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067##
##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072##
##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087##
##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092##
##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097##
##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102##
##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107##
##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112##
##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117##
##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122##
##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127##
##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132##
##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137##
##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142##
##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147##
##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152##
##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157##
##STR00158## ##STR00159##
[0047] The compounds according to the invention can be prepared by
synthesis steps known to the person skilled in the art, such as,
for example, bromination, Suzuki coupling, Ullmann coupling,
Hartwig-Buchwald coupling, etc. Suitable synthesis processes are
depicted in general terms in Scheme 1 below.
##STR00160##
[0048] The compounds of formula (1) may be synthesized as described
above. In a first step, a heteroaromatic group Ar.sup.1 comprising
a nitrogen atom is bonded via a C--C coupling to a heterocycle
comprising a pyrrole group (for example via a nucleophilic aromatic
substitution). The obtained compound reacts then with a
triarylborane compound in order to obtain the compounds of formula
(1).
[0049] The present invention therefore furthermore relates to a
process for the synthesis of the compounds according to the
invention comprising the following steps:
a) A heteroaromatic group Ar.sup.1 comprising at least one nitrogen
is bonded to a heterocycle comprising a pyrrole moiety via a C--C
coupling in order to obtain a compound of formula Int:
##STR00161##
b) The compound of formula Int reacts with a triarylborane
B(Ar.sup.B).sub.3 so that a compound of formula (1) is
obtained:
##STR00162##
where the symbols Ar.sup.1, Ar.sup.2, Ar.sup.B and X have the same
meaning as above.
[0050] Scheme 2 represents an alternative process for the synthesis
of the compounds according to the invention.
##STR00163##
[0051] For the processing of the compounds according to the
invention from the liquid phase, for example by spin coating or by
printing processes, formulations of the compounds according to the
invention are necessary. These formulations can be, for example,
solutions, dispersions or emulsions. It may be preferred to use
mixtures of two or more solvents for this purpose. Suitable and
preferred solvents are, for example, toluene, anisole, o-, m- or
p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF,
methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in
particular 3-phenoxytoluene, (-)-fenchone,
1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene,
1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol,
2-pyrrolidinone, 3-methylanisole, 4-methylanisole,
3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone,
.alpha.-terpineol, benzothiazole, butyl benzoate, cumene,
cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin,
dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP,
p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether,
diethylene glycol butyl methyl ether, triethylene glycol butyl
methyl ether, diethylene glycol dibutyl ether, triethylene glycol
dimethyl ether, diethylene glycol-monobutyl ether, tripropylene
glycol dimethyl ether, tetraethylene glycol dimethyl ether,
2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene,
octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or mixtures of
these solvents.
[0052] The present invention therefore furthermore relates to a
formulation comprising a compound according to the invention and at
least one further compound. The further compound may be, for
example, a solvent, in particular one of the above-mentioned
solvents or a mixture of these solvents. However, the further
compound may also be at least one further organic or inorganic
compound which is likewise employed in the electronic device, for
example an emitting compound, in particular a phosphorescent
dopant, and/or a further matrix material. Suitable emitting
compounds and further matrix materials are indicated below in
connection with the organic electroluminescent device. This further
compound may also be polymeric.
[0053] The compounds and mixtures according to the invention are
suitable for use in an electronic device. An electronic device here
is taken to mean a device which comprises at least one layer which
comprises at least one organic compound. However, the component
here may also comprise inorganic materials or also layers built up
entirely from inorganic materials.
[0054] The present invention therefore furthermore relates to the
use of the compounds or mixtures according to the invention in an
electronic device, in particular in an organic electroluminescent
device.
[0055] The present invention again furthermore relates to an
electronic device comprising at least one of the compounds or
mixtures according to the invention mentioned above. The
preferences stated above for the compound also apply to the
electronic devices.
[0056] The electronic device is preferably selected from the group
consisting of organic electroluminescent devices (OLEDs, PLEDs),
organic integrated circuits (O-ICs), organic field-effect
transistors (O-FETs), organic thin-film transistors (O-TFTs),
organic light-emitting transistors (O-LETs), organic solar cells
(O-SCs), organic dye-sensitised solar cells, organic optical
detectors, organic photoreceptors, organic field-quench devices
(O-FQDs), light-emitting electrochemical cells (LECs), organic
laser diodes (O-lasers) and "organic plasmon emitting devices" (D.
M. Koller et al., Nature Photonics 2008, 1-4), preferably organic
electroluminescent devices (OLEDs, PLEDs), in particular
phosphorescent OLEDs.
[0057] The organic electroluminescent device comprises a cathode,
an anode and at least one emitting layer. Apart from these layers,
it may also comprise further layers, for example in each case one
or more hole-injection layers, hole-transport layers, hole-blocking
layers, electron-transport layers, electron-injection layers,
exciton-blocking layers, electron-blocking layers and/or
charge-generation layers. It is likewise possible for interlayers,
which have, for example, an exciton-blocking function, to be
introduced between two emitting layers. However, it should be
pointed out that each of these layers does not necessarily have to
be present. The organic electroluminescent device here may comprise
one emitting layer or a plurality of emitting layers. If a
plurality of emission layers are present, these preferably have in
total a plurality of emission maxima between 380 nm and 750 nm,
resulting overall in white emission, i.e. various emitting
compounds which are able to fluoresce or phosphoresce are used in
the emitting layers. Particular preference is given to systems
having three emitting layers, where the three layers exhibit blue,
green and orange or red emission (for the basic structure see, for
example, WO 2005/011013). These can be fluorescent or
phosphorescent emission layers or hybrid systems, in which
fluorescent and phosphorescent emission layers are combined with
one another.
[0058] The compound according to the invention in accordance with
the embodiments indicated above can be employed in various layers,
depending on the precise structure. Preference is given to an
organic electroluminescent device comprising a compound of the
formula (1) or in accordance with the preferred embodiments as
matrix material for fluorescent emitters, phosphorescent emitters
or emitters showing TADF (Thermally Activated Delayed
Fluorescence), in particular for phosphorescent emitters, and/or in
an electron-transport layer and/or in an electron-blocking or
exciton-blocking layer and/or in a hole-transport layer, depending
on the precise substitution. The preferred embodiments indicated
above also apply to the use of the materials in organic electronic
devices.
[0059] In a preferred embodiment of the invention, the compound of
the formula (1) or in accordance with the preferred embodiments is
employed as matrix material for a fluorescent or phosphorescent
compound, in particular for a phosphorescent compound, in an
emitting layer. The organic electroluminescent device here may
comprise one emitting layer or a plurality of emitting layers,
where at least one emitting layer comprises at least one compound
according to the invention as matrix material.
[0060] If the compound of the formula (1) or in accordance with the
preferred embodiments is employed as matrix material for an
emitting compound in an emitting layer, it is preferably employed
in combination with one or more phosphorescent materials (triplet
emitters). Phosphorescence in the sense of this invention is taken
to mean the luminescence from an excited state having spin
multiplicity >1, in particular from an excited triplet state.
For the purposes of this application, all luminescent
transition-metal complexes and luminescent lanthanide complexes, in
particular all iridium, platinum and copper complexes, are to be
regarded as phosphorescent compounds.
[0061] Preferably, when the compounds of the formula (1) or in
accordance with the preferred embodiments are employed as matrix
materials for an emitting compound in an emitting layer, they are
preferably employed in combination with one or more phosphorescent
material (triplet emitters), where the phosphorescent material has
an emission wavelength comprised between 550 nm to 680 nm, which
corresponds to the red emission field.
[0062] The mixture comprising the compound of the formula (1) or in
accordance with the preferred embodiments and the emitting compound
comprises between 99 and 1% by vol., preferably between 98 and 10%
by vol., particularly preferably between 97 and 60% by vol., in
particular between 95 and 80% by vol., of the compound of the
formula (1) or in accordance with the preferred embodiments, based
on the entire mixture comprising emitter and matrix material.
Correspondingly, the mixture comprises between 1 and 99% by vol.,
preferably between 2 and 90% by vol., particularly preferably
between 3 and 40% by vol., in particular between 5 and 20% by vol.,
of the emitter, based on the entire mixture comprising emitter and
matrix material.
[0063] A further preferred embodiment of the present invention is
the use of the compound of the formula (1) or in accordance with
the preferred embodiments as matrix material for a phosphorescent
emitter in combination with a further matrix material. Particularly
suitable matrix materials which can be employed in combination with
the compounds of the formula (1) or in accordance with the
preferred embodiments are aromatic ketones, aromatic phosphine
oxides or aromatic sulfoxides or sulfones, for example in
accordance with WO 2004/013080, WO 2004/093207, WO 2006/005627 or
WO 2010/006680, triarylamines, carbazole derivatives, for example
CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives
disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP
1205527 or WO 2008/086851, indolocarbazole derivatives, for example
in accordance with WO 2007/063754 or WO 2008/056746,
indenocarbazole derivatives, for example in accordance with WO
2010/136109 and WO 2011/000455, azacarbazole derivatives, for
example in accordance with EP 1617710, EP 1617711, EP 1731584, JP
2005/347160, bipolar matrix materials, for example in accordance
with WO 2007/137725, silanes, for example in accordance with WO
005/111172, azaboroles or boronic esters, for example in accordance
with WO 2006/117052, triazine derivatives, for example in
accordance with WO 2010/015306, WO 2007/063754 or WO 2008/056746,
zinc complexes, for example in accordance with EP 652273 or WO
2009/062578, diazasilole or tetraazasilole derivatives, for example
in accordance with WO 2010/054729, diazaphosphole derivatives, for
example in accordance with WO 2010/054730, bridged carbazole
derivatives, for example in accordance with US 2009/0136779, WO
2010/050778, WO 2011/042107, WO 2011/088877 or in accordance with
EP 11003232.3, triphenylene derivatives, for example in accordance
with WO 2012/048781, or lactams, for example in accordance with WO
2011/116865 or WO 2011/137951. A further phosphorescent emitter
which emits at shorter wavelength than the actual emitter may
likewise be present in the mixture as co-host.
[0064] Preferred co-host materials are triarylamine derivatives, in
particular monoamines, lactams, carbazole derivatives and
indenocarbazole derivatives.
[0065] Suitable phosphorescent compounds (=triplet emitters) are,
in particular, compounds which emit light, preferably in the
visible region, on suitable excitation and in addition contain at
least one atom having an atomic number greater than 20, preferably
greater than 38 and less than 84, particularly preferably greater
than 56 and less than 80, in particular a metal having this atomic
number. The phosphorescent emitters used are preferably compounds
which contain copper, molybdenum, tungsten, rhenium, ruthenium,
osmium, rhodium, iridium, palladium, platinum, silver, gold or
europium, in particular compounds which contain iridium or
platinum. For the purposes of the present invention, all
luminescent compounds which contain the above-mentioned metals are
regarded as phosphorescent compounds.
[0066] Examples of the emitters described above are revealed by the
applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO
2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO
05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO
2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO
2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO
2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO
2014/094962, WO 2014/094961, WO 2014/094960 or WO 2016/124304. In
general, all phosphorescent complexes as used in accordance with
the prior art for phosphorescent OLEDs and as are known to the
person skilled in the art in the area of organic
electroluminescence are suitable, and the person skilled in the art
will be able to use further phosphorescent complexes without
inventive step.
[0067] Suitable phosphorescent materials (=triplet emitters) that
can be advantageously combined with the compounds of formula (1)
are, as mentioned above, compounds which emit a red light on
suitable excitation, which means phosphorescent materials having an
excited triplet state level (T1) comprised between 550 and 680
nm.
[0068] In a further embodiment of the invention, the organic
electroluminescent device according to the invention does not
comprise a separate hole-injection layer and/or hole-transport
layer and/or hole-blocking layer and/or electron-transport layer,
i.e. the emitting layer is directly adjacent to the hole-injection
layer or the anode, and/or the emitting layer is directly adjacent
to the electron-transport layer or the electron-injection layer or
the cathode, as described, for example, in WO 2005/053051. It is
furthermore possible to use a metal complex which is identical or
similar to the metal complex in the emitting layer as
hole-transport or hole-injection material directly adjacent to the
emitting layer, as described, for example, in WO 2009/030981.
[0069] It is furthermore possible to employ the compounds according
to the invention in a hole-blocking or electron-transport layer.
This applies, in particular, to compounds according to the
invention which do not have a carbazole structure. These may
preferably also be substituted by one or more further
electron-transporting groups, for example benzimidazole groups.
[0070] In the further layers of the organic electroluminescent
device according to the invention, it is possible to use all
materials as usually employed in accordance with the prior art. The
person skilled in the art will therefore be able, without inventive
step, to employ all materials known for organic electroluminescent
devices in combination with the compounds of the formula (1) or in
accordance with the preferred embodiments.
[0071] Preference is furthermore given to an organic
electroluminescent device, characterised in that one or more layers
are applied by means of a sublimation process, in which the
materials are vapour-deposited in vacuum sublimation units at an
initial pressure of less than 10.sup.-5 mbar, preferably less than
10.sup.-6 mbar. However, it is also possible for the initial
pressure to be even lower or higher, for example less than
10.sup.-7 mbar.
[0072] Preference is likewise given to an organic
electroluminescent device, characterised in that one or more layers
are applied by means of the OVPD (organic vapour phase deposition)
process or with the aid of carrier-gas sublimation, in which the
materials are applied at a pressure between 10.sup.-5 mbar and 1
bar. A special case of this process is the OVJP (organic vapour jet
printing) process, in which the materials are applied directly
through a nozzle and thus structured (for example M. S. Arnold et
al., Appl. Phys. Lett. 2008, 92, 053301).
[0073] Preference is furthermore given to an organic
electroluminescent device, characterised in that one or more layers
are produced from solution, such as, for example, by spin coating,
or by means of any desired printing process, such as, for example,
ink-jet printing, LITI (light induced thermal imaging, thermal
transfer printing), screen printing, flexographic printing, offset
printing or nozzle printing. Soluble compounds, which are obtained,
for example, by suitable substitution, are necessary for this
purpose.
[0074] Also possible are hybrid processes, in which, for example,
one or more layers are applied from solution and one or more
further layers are applied by vapour deposition. Thus, it is
possible, for example, to apply the emitting layer from solution
and to apply the electron-transport layer by vapour deposition.
[0075] These processes are generally known to the person skilled in
the art and can be applied by him without inventive step to organic
electroluminescent devices comprising the compounds according to
the invention.
[0076] The compounds according to the invention generally have very
good properties on use in organic electroluminescent devices. In
particular, the lifetime on use of the compounds according to the
invention in organic electroluminescent devices is significantly
better compared with similar compounds in accordance with the prior
art. The other properties of the organic electroluminescent device,
in particular the efficiency and the voltage, are likewise better
or at least comparable. Furthermore, the compounds have a high
glass transition temperature and high thermal stability.
[0077] The invention will now be explained in greater detail by the
following examples, without wishing to restrict it thereby.
A) SYNTHESES EXAMPLES
[0078] The following syntheses are carried out, unless indicated
otherwise, under a protective-gas atmosphere in dried solvents. The
solvents and reagents can be purchased, for example, from
Sigma-ALDRICH or ABCR. The corresponding CAS numbers are also
indicated in each case from the compounds known from the
literature.
a) 1-(pyridine-2-yl)-9H-carbazole
##STR00164##
[0080] 15 g (61 mmol) of 1-bromo-9H-carbazole are dissolved in 1000
ml of anhydrous THF under a nitrogen atmosphere and cooled to
-78.degree. C. After the addition of 130 mL (240 mmol) of a
solution of t-butyllithium (1.9 M) in pentane, the solution is
stirred for about 2 hours until it reaches -20.degree. C. Then, 5.7
g (73 mmol) of pyrimidine are injected in the reaction mixture,
which is further stirred for about 2 hours, until room temperature
is reached. After addition of 300 ml of water, the extraction is
carried out three times using 300 ml of ethyl acetate each time.
The combined organic phases are dried over sodium sulfate, the
solvent is removed under vacuum and the residue is purified by
silica gel column chromatography using dichloromethane/petroleum
ether/TEA 5:5:1.
[0081] The following compounds are prepared analogously:
TABLE-US-00002 Educt 1 Educt 2 Product Yield a1 ##STR00165##
##STR00166## ##STR00167## 40% a2 ##STR00168## ##STR00169##
##STR00170## 34% a3 ##STR00171## ##STR00172## ##STR00173## 40% a4
##STR00174## ##STR00175## ##STR00176## 41% a5 ##STR00177##
##STR00178## ##STR00179## 43% a6 ##STR00180## ##STR00181##
##STR00182## 39% a7 ##STR00183## ##STR00184## ##STR00185## 38%
b) 1-(1-phenyl-1H-benzoimidazol-2-yl)-9H-carbazole
##STR00186##
[0083] First, 37.3 g (152 mmol) of 1-bromo-carbazole, 42.8 g (180
mmol) of B-(1-phenyl-1H-benzimidazol-2-yl)-boronic acid and 36 g
(340 mmol) of sodium carbonate are suspended in 1000 mL of ethylene
glycol dimethyl ether and 280 mL of water.
[0084] 1.8 g (1.5 mmol) of
tetrakies(triphenylphosphin)-palladium(0) are added to this
suspension, and the reaction mixture is heated under refluxed for
16 h. After cooling, the organic phase is separated off, filtered
over silica gel, washed three times with 200 mL of water and then
concentrated to dryness. The product is purified by means of column
chromatography on silica gel with toluene/heptane (1:2).
[0085] The yield is 36 g (100 mmol), corresponding to 68% of the
theory.
[0086] The following compounds are prepared analogously:
TABLE-US-00003 Educt 1 Educt 2 b1 ##STR00187## ##STR00188## b2
##STR00189## ##STR00190## b3 ##STR00191## ##STR00192## b4
##STR00193## ##STR00194## b5 ##STR00195## ##STR00196## b6
##STR00197## ##STR00198## b7 ##STR00199## ##STR00200## b8
##STR00201## ##STR00202## b9 ##STR00203## ##STR00204## b10
##STR00205## ##STR00206## b11 ##STR00207## ##STR00208## b12
##STR00209## ##STR00210## b13 ##STR00211## ##STR00212## 14b
##STR00213## ##STR00214## Product Yield b1 ##STR00215## 77% b2
##STR00216## 76% b3 ##STR00217## 74% b4 ##STR00218## 69% b5
##STR00219## 72% b6 ##STR00220## 79% b7 ##STR00221## 68% b8
##STR00222## 82% b9 ##STR00223## 67% b10 ##STR00224## 75% b11
##STR00225## 68% b12 ##STR00226## 56% b13 ##STR00227## 61% 14b
##STR00228## 48%
c)
1-[4-(9-phenyl-9H-carbazol-3-yl)-pyridin-2-yl]-9H-beta-carboline
##STR00229##
[0088] 50 g (155 mmol) of
1-(4-bromo-pyridin-2-yl)-9H-beta-carboline, 50 g (172 mmol) of
N-phenyl-carbazole-3-boronic acid and 36 g (340 mmol) of sodium
carbonate are suspended in 1000 mL of ethylene glycol dimethyl
ether r and 280 mL of water.
[0089] 1.8 g (1.5 mmol) of
tetrakies(triphenylphosphin)-palladium(0) are added to this
suspension, and the reaction mixture is heated under refluxed for
16 h. After cooling, the organic phase is separated off, filtered
over silica gel, washed three times with 200 mL of water and then
concentrated to dryness. The product is purified by means of column
chromatography on silica gel with toluene/heptane (1:2).
[0090] The yield is 53 g (100 mmol), corresponding to 71% of
theory.
[0091] The following compound is prepared analogously:
TABLE-US-00004 Educt 1 Educt 2 c1 ##STR00230## ##STR00231## Product
Yield c1 ##STR00232## 61%
d) 9-diphenylboranyl-1-pyridin-2-yl-9H-carbazole
##STR00233##
[0093] 52 g (215 mmol) of 1-pyridin-2-yl-9H-carbazole and 78 g (320
mmol) of triphenylborane are dissolved under a protecting gas in
3000 ml of dry toluene and the mixture is boiled under reflux for
50 h. The solvent is distilled off under vacuum, the product is
purified by chromatography (EA/hexane, 1:5) and finally sublimed
(purity 99.9%) in high vacuum (p=5.times.10.sup.-7 mbar). The yield
is 51 g (124 mmol), 59% of the theory.
[0094] The following compounds are prepared analogously:
TABLE-US-00005 Educt 1 Educt 2 Product Yield d1 ##STR00234##
##STR00235## ##STR00236## 60% d2 ##STR00237## ##STR00238##
##STR00239## 67% d3 ##STR00240## ##STR00241## ##STR00242## 61% d4
##STR00243## ##STR00244## ##STR00245## 44% d5 ##STR00246##
##STR00247## ##STR00248## 58% d6 ##STR00249## ##STR00250##
##STR00251## 54% d7 ##STR00252## ##STR00253## ##STR00254## 51% d8
##STR00255## ##STR00256## ##STR00257## 56% d9 ##STR00258##
##STR00259## ##STR00260## 52% d10 ##STR00261## ##STR00262##
##STR00263## 54% d11 ##STR00264## ##STR00265## ##STR00266## 59% d12
##STR00267## ##STR00268## ##STR00269## 50% d13 ##STR00270##
##STR00271## ##STR00272## 56% d14 ##STR00273## ##STR00274##
##STR00275## 60% d15 ##STR00276## ##STR00277## ##STR00278## 62% d16
##STR00279## ##STR00280## ##STR00281## 62% d17 ##STR00282##
##STR00283## ##STR00284## 60% d19 ##STR00285## ##STR00286##
##STR00287## 63% d20 ##STR00288## ##STR00289## ##STR00290## 62% d21
##STR00291## ##STR00292## ##STR00293## 57% d22 ##STR00294##
##STR00295## ##STR00296## 56% d23 ##STR00297## ##STR00298##
##STR00299## 56% d24 ##STR00300## ##STR00301## ##STR00302## 58% d25
##STR00303## ##STR00304## ##STR00305## 48% d26 ##STR00306##
##STR00307## ##STR00308## 42% d27 ##STR00309## ##STR00310##
##STR00311## 61% d28 ##STR00312## ##STR00313## ##STR00314## 53% d29
##STR00315## ##STR00316## ##STR00317## 57% d30 ##STR00318##
##STR00319## ##STR00320## 59% d31 ##STR00321## ##STR00322##
##STR00323## 45% d32 ##STR00324## ##STR00325## ##STR00326## 53% d33
##STR00327## ##STR00328## ##STR00329## 51% d34 ##STR00330##
##STR00331## ##STR00332## 45% d35 ##STR00333## ##STR00334##
##STR00335## 47% d36 ##STR00336## ##STR00337## ##STR00338## 52% d37
##STR00339## ##STR00340## ##STR00341## 50% d38 ##STR00342##
##STR00343## ##STR00344## 41% d40 ##STR00345## ##STR00346##
##STR00347## 43% d41 ##STR00348## ##STR00349## ##STR00350## 56% d42
##STR00351## ##STR00352## ##STR00353## 49% d43 ##STR00354##
##STR00355## ##STR00356## 55% d44 ##STR00357## ##STR00358##
##STR00359## 65% d45 ##STR00360## ##STR00361## ##STR00362## 41% d46
##STR00363## ##STR00364## ##STR00365## 43% d47 ##STR00366##
##STR00367## ##STR00368## 55%
B) FABRICATION OF OLEDS
[0095] The following examples E1 to E6 (see Table 1) show data of
various OLEDs.
[0096] Substrate pre-treatment of examples E1-E6: Glass plates with
structured ITO (50 nm, indium tin oxide) form the substrates on
which the OLEDs are processed. Before evaporation of the OLED
materials, the substrates are pre-baked for 15 minutes at
250.degree. C., followed by an O.sub.2 and subsequent Argon plasma
treatment.
[0097] The OLEDs have in principle the following layer structure:
substrate/hole-transport layer (HTL)/optional interlayer
(IL)/electron-blocking layer (EBL)/emission layer (EML)/optional
hole-blocking layer (HBL)/electron-transport layer (ETL)/optional
electron-injection layer (EIL) and finally a cathode. The cathode
is formed by an aluminium layer with a thickness of 100 nm. The
exact layer structure is denoted in Table 1. The materials used for
the OLED fabrication are presented in Table 2.
[0098] All materials are applied by thermal vapour deposition in a
vacuum chamber. The emission layer here always consists of at least
one matrix material (host material) and an emitting dopant
(emitter), which is admixed with the matrix material or matrix
materials in a certain proportion by volume by co-evaporation. An
expression such as IC1:M1:TEG1 (55%:35%:10%) here means that
material IC1 is present in the layer in a proportion by volume of
55%, M1 is present in the layer in a proportion of 35% and TEG1 is
present in the layer in a proportion of 10%. Analogously, the
electron-transport layer may also consist of a mixture of two
materials.
[0099] The OLEDs are characterised by standard methods. The
electroluminescence (EL) spectra are recorded at a luminous density
of 1000 cd/m.sup.2 and the CIE 1931 x an y coordinates are then
calculated from the EL spectrum.
TABLE-US-00006 TABLE 1 OLED layer structure HIL HTL EBL EML ETL
Bsp. Dicke Dicke Dicke Dicke Dicke E1 HATCN SpMA1 SpMA3
IC5:EG1:TER5 ST2:LiQ 5 nm 125 nm 10 nm (45%:40%:5%) (50%:50%) 40 nm
35 nm E2 HATCN SpMA1 SpMA3 IC5:EG2:TER5 ST2:LiQ 5 nm 125 nm 10 nm
(45%:40%:5%) (50%:50%) 40 nm 35 nm E3 HATCN SpMA1 SpMA3
IC5:EG3:TER5 ST2:LiQ 5 nm 125 nm 10 nm (45%:40%:5%) (50%:50%) 40 nm
35 nm E4 HATCN SpMA1 SpMA3 IC5:EG4:TER5 ST2:LiQ 5 nm 125 nm 10 nm
(45%:40%:5%) (50%:50%) 40 nm 35 nm E5 HATCN SpMA1 SpMA3
IC5:EG5:TER5 ST2:LiQ 5 nm 125 nm 10 nm (45%:40%:5%) (50%:50%) 40 nm
35 nm E6 HATCN SpMA1 SpMA3 IC5:EG6:TER5 ST2:LiQ 5 nm 125 nm 10 nm
(45%:40%:5%) (50%:50%) 40 nm 35 nm
TABLE-US-00007 TABLE 2 Chemical structures of the OLED materials
##STR00369## HATCN ##STR00370## SpMA1 ##STR00371## SpMA3
##STR00372## LiQ ##STR00373## ST2 ##STR00374## TER5 ##STR00375##
IC5 ##STR00376## EG1 ##STR00377## EG2 ##STR00378## EG3 ##STR00379##
EG4 ##STR00380## EG5 ##STR00381## EG6
[0100] The examples E1-E6 show data of inventive OLEDs.
Use of Inventive Compounds as Host Material in Phosphorescent
OLEDs
[0101] The use of the inventive materials EG1 to EG6 as host
material in phosphorescent red OLEDs (experiments E1 to E6) results
in an electroluminescent emission with the color coordinates
CIEx=0.67 and CIEy=0.33. This shows that the inventive materials
are suitable for the use in OLEDs.
* * * * *